CN108084667B - A kind of modified microcrystalline cellulose enhancing soybean oil based resin composite material and preparation method - Google Patents
A kind of modified microcrystalline cellulose enhancing soybean oil based resin composite material and preparation method Download PDFInfo
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- CN108084667B CN108084667B CN201810037582.9A CN201810037582A CN108084667B CN 108084667 B CN108084667 B CN 108084667B CN 201810037582 A CN201810037582 A CN 201810037582A CN 108084667 B CN108084667 B CN 108084667B
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- microcrystalline cellulose
- soybean oil
- composite material
- based resin
- oil based
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
Abstract
The invention discloses a kind of modified microcrystalline celluloses to enhance soybean oil based resin composite material and preparation method.First microcrystalline cellulose is modified using modifying agent, catalyst, the modified microcrystalline cellulose of acquisition is uniformly mixed with soybean oil resin, initiator, solvent again, inject mold cured molding, it is made with high-performance and environmental-friendly modified microcrystalline cellulose enhances soybean oil based thermoset applications composite material, resulting composite material has good bending strength, bending modulus and water resistance.
Description
Technical field
The invention belongs to fiber-resin composite technical fields, and in particular to a kind of modified microcrystalline cellulose enhancing
Soybean oil based resin composite material and preparation method.
Background technique
In composite system, most common thermosetting resin mainly has epoxy resin, phenolic resin and unsaturation poly-
Ester resin.Generally, these thermosetting resins have good mechanical property, chemical-resistance and processing performance, but are using
Environmental problem and air pollution problems inherent brought by the volatilization of noxious material (such as formaldehyde, styrene etc.) have caused greatly in the process
Concern.People are forced to be sought for and develop newly renewable in addition, the continuous consumption of petroleum-based sources and price rise problem
Bio-based resin.Epoxy soybean oil acrylate (AESO) is to react to obtain with acrylic acid after epoxidation by soybean oil, at present
Has mass production on the market, raw material sources are extensive, cheap, have been widely used in coating, degradable foamed material
Equal fields.
Cellulose is one of yield maximum and reproducible bio-based polymers in nature, derive from extensively plant,
Bacterium, shell etc..Microcrystalline cellulose (MCC) is a kind of hydrocellulose, is made of a large amount of cellulose crystallite body, has life
The advantages that Biodegradable, renewable, low-density, cheap, good mechanical property, therefore can be used for polymer matrix composites
Reinforcement.However, the surface MCC has very strong hydrophily, the bad dispersibility in most of non-polar polymers leads to fiber-
The interface cohesion of matrix is weak, to influence the reinforcing effect to resin matrix.
This seminar is with cheap soybean oil derivative --- and epoxy soybean oil acrylate (AESO) is matrix, with
Microcrystalline cellulose (MCC) is reinforcement, prepares MCC/AESO " Quan Lvse " composite material.However, due to the surface MCC and AESO tree
Rouge can reaction active groups it is few, the two interface cohesion is poor, while MCC surface hydrophilicity is strong, the bad dispersibility in resin matrix
The disadvantages of, need to be modified the surface MCC, introduce can with resin matrix generate Covalent bonding together functional group, improve MCC with
The interface cohesion of AESO enhances the properties of MCC/AESO composite material.Pass through methacrylic anhydride and MCC surface-active hydroxyl
C=C double bond of methacrylic anhydride can be connected to the surface MCC, to reduce MCC surface hydrophilicity, increased simultaneously by the reaction of base
The reactivity of MCC and AESO improves the two interface cohesion.Therefore, prepared microcrystalline cellulose/soybean oil base according to the present invention
Thermoset ting resin composite have the characteristics that it is environmental-friendly, at low cost, and composite material have good bending strength, bending
Modulus and water resistance.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of modified microcrystalline cellulose enhancing soybean oil base
Resin composite materials and preparation method thereof.The program solves the shortage of petroleum base resin raw material sources, expensive, preparation process
The problems such as environmental pollution caused by middle noxious material release, prepare high-performance and environmental-friendly microcrystalline cellulose/soybean
Oil-based resin composite material, resulting composite material have good bending strength, bending modulus and water resistance.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of modified microcrystalline cellulose is by solvent, modifying agent, catalyst and microcrystalline cellulose in ultrasonic wave booster action
Lower modification forms, and the modifying agent is methacrylic anhydride, and the mass ratio of modifying agent and microcrystalline cellulose is 0.5 ~ 1.5:1.
The solvent is n,N-Dimethylformamide；The catalyst is 4-dimethylaminopyridine.
A method of it preparing modified microcrystalline cellulose as described above: microcrystalline cellulose, modifying agent and catalyst is set
In the flask containing solvent；Then flask is placed in ultrasound bath pot, magnetic agitation 500r/min, 60 DEG C of reactions 2
H, ultrasonic power are 80 W；Filtering obtained solid product is through acetone, saturation NaHCO after reaction3Solution and distilled water are anti-
After cleaning filter 23 ~ 5 time again, 80 DEG C of 24 h of drying of vacuum are to get modified microcrystalline cellulose.
It is a kind of using modified microcrystalline cellulose as described above prepare enhancing soybean oil based resin composite material: including with
The raw material of lower parts by weight: 20 ~ 40 parts of modified microcrystalline cellulose, 80 ~ 60 parts of soybean oil based resin, 1 ~ 7 part of initiator.
The preferable composite material of raw material proportioning includes the raw material of following parts by weight: 30 parts of modified microcrystalline cellulose, soybean
70 parts of oil-based resin, 3 parts of initiator.
The soybean oil based resin is epoxy soybean oil acrylate；The initiator is the tertiary fourth of perbenzoic acid
Ester.
A method of it preparing composite material as described above: modified microcrystalline cellulose is dispersed under ultrasonic wave auxiliary
In acetone, and with 5 min of speed magnetic agitation of 500r/min, ultrasonic power is 80 W, forms dispersion liquid；It then will be big
Soybean oil based resin is added in dispersion liquid, increases temperature to 80 DEG C, continues to stir 10 min to remove acetone；It then cools to room temperature
Afterwards, initiator is added, and stirs 2 min, obtains cellulose-resin mixture liquor；Then cellulose-resin mixture liquor is injected into silicon
Sealing rubber die molding, solidification temperature are 100 ~ 160 DEG C, and the time is 2 ~ 6 h；After cooling mold and take out sample to get modification
Microcrystalline cellulose enhances soybean oil based resin composite material.
The beneficial effects of the present invention are:
The present invention is modified through methacrylic anhydride by microcrystalline cellulose (MCC), can be by C=C double bond of methacrylic anhydride
It is connected to the surface MCC, to reduce MCC surface hydrophilicity, while increasing the reactivity of MCC and AESO, improves the two interface cohesion,
Prepared microcrystalline cellulose/soybean oil based thermoset applications composite material has the characteristics that environmental-friendly, at low cost；With do not change
Property microcrystalline cellulose/AESO resin composite materials compare, using methacrylic anhydride modified microcrystalline cellulose composite material have
There are superior bending strength, bending modulus and water resistance.
Detailed description of the invention
Fig. 1 is the bending strength of modified microcrystalline cellulose enhancing soybean oil based resin composite material, wherein Control table
Show unmodified microcrystalline cellulose enhancing soybean oil based resin composite material；0.5 ~ 1.5 respectively indicates crystallite modifying agent and cellulose
Mass ratio be 0.5 ~ 1.5 composite material；Rectangular column upper and lower horizontal line indicates the standard deviation of data mean value in figure；
Fig. 2 is the bending modulus of modified microcrystalline cellulose enhancing soybean oil based resin composite material；
Fig. 3 is the bending strain of modified microcrystalline cellulose enhancing soybean oil based resin composite material；
Fig. 4 is the water absorption rate of modified microcrystalline cellulose enhancing soybean oil based resin composite material；Rectangular column upper and lower in figure
The standard deviation of horizontal line expression data mean value.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
Raw material: microcrystalline cellulose (average particle size is 50 μm) is purchased from Thermo Fisher Scientific Inc.；Epoxy soybean
(average molecular weight is 1200 g/mol to oily acrylate (AESO)；Viscosity (25 DEG C): 18000 ~ 32000 mPas；Acid value:
≤ 10 mg KOH/g；Polymerization inhibitor: 3500 ~ 4500 ppm metoxyphenols), n,N-Dimethylformamide (DMF), metering system
Acid anhydrides (MAA), 4-dimethylaminopyridine (DMAP) and peroxidized t-butyl perbenzoate (TBPB) are purchased from Sigma-Aldrich
(Shanghai) trade Co., Ltd.
Modified microcrystalline cellulose enhances soybean oil based resin composite material:
The modifying process of modified microcrystalline cellulose are as follows: by the microcrystalline cellulose of 10 g, the methacrylic anhydride of 5 g and 0.5
The 4-dimethylaminopyridine of g is placed in the flask of the dimethylformamide containing 150 mL；Flask is then placed in ultrasonic water
In bath, 500 r/min of magnetic agitation, 60 DEG C of 2 h of reaction, ultrasonic power are 80 W；Solid is obtained by filtration after reaction
Product is through acetone, saturation NaHCO380 DEG C of 24 h of drying of vacuum are after solution and distilled water clean filtering 4 times repeatedly to get modification
Microcrystalline cellulose.
Composite material and preparation method thereof: the initiation of the modified microcrystalline cellulose of 30 g, the soybean oil based resin of 70 g, 1.4 g
Injection silica gel mould forms to obtain after agent and acetone are mixed evenly, the specific steps are as follows: by the modification of microcrystalline fiber of 30 g
Element is dispersed in the acetone of 100 mL under ultrasonic water bath auxiliary, and 500 r/min of magnetic agitation, 5 min, ultrasonic power are
80 W；Then the soybean oil based resin of 70 g is added and increases temperature to 80 DEG C, continues to stir 10 min to remove acetone；
1.4 g of initiator is added after being cooled to room temperature and stirs 2 min, then by cellulose-resin mixture liquor injection silica gel mould at
Type, solidification process is warming up to 160 DEG C after being 120 DEG C of 2 h of heating continues to solidify 4 h；After cooling mold and take out sample,
Enhance soybean oil based resin composite material up to modified microcrystalline cellulose.
In the preparation process, the amount ratio of modifying agent and microcrystalline cellulose is in mass ratio 0.5:1；Modification of microcrystalline is fine
Dimension element is 3:7 with soybean oil based resin mass ratio；The dosage of initiator is the 2% of resin quality.
Embodiment 2
Raw material: microcrystalline cellulose (average particle size is 50 μm) is purchased from Thermo Fisher Scientific Inc.；Epoxy soybean
(average molecular weight is 1200 g/mol to oily acrylate (AESO)；Viscosity (25 DEG C): 18000 ~ 32000 mPas；Acid value:
≤ 10 mg KOH/g；Polymerization inhibitor: 3500 ~ 4500 ppm metoxyphenols), n,N-Dimethylformamide (DMF), metering system
Acid anhydrides (MAA), 4-dimethylaminopyridine (DMAP) and peroxidized t-butyl perbenzoate (TBPB) are purchased from Sigma-Aldrich
(Shanghai) trade Co., Ltd.
Modified microcrystalline cellulose enhances soybean oil based resin composite material:
The modifying process of modified microcrystalline cellulose are as follows: by the microcrystalline cellulose of 10 g, the methacrylic anhydride of 10 g and 0.5
The 4-dimethylaminopyridine of g is placed in the flask of the dimethylformamide containing 150 mL；Flask is then placed in ultrasonic water
In bath, 500 r/min of magnetic agitation, 60 DEG C of 2 h of reaction, ultrasonic power are 80 W；Solid is obtained by filtration after reaction
Product is through acetone, saturation NaHCO380 DEG C of 24 h of drying of vacuum are after solution and distilled water clean filter 23 time repeatedly to get modification
Microcrystalline cellulose.
Composite material and preparation method thereof: the initiation of the modified microcrystalline cellulose of 30 g, the soybean oil based resin of 70 g, 1.4 g
Injection silica gel mould forms to obtain after agent and acetone are mixed evenly, the specific steps are as follows: by the modification of microcrystalline fiber of 30 g
Element is dispersed in the acetone of 100 mL under ultrasonic water bath auxiliary, and magnetic stirs 500 r/min, 5 min, ultrasonic power 80
W；Then the soybean oil based resin of 70 g is added and increases temperature to continuing to stir 10 min at 80 DEG C to remove acetone；It is cold
But to 1.4 g of initiator is added after room temperature and stirs cellulose-resin mixture liquor injection silica gel mould molding after 2 min, Gu
Change process is warming up to 160 DEG C and continues to solidify 4 h after being 120 DEG C of 2 h of heating；After cooling mold and take out sample to get
Modified microcrystalline cellulose enhances soybean oil based resin composite material.
In the preparation process, the amount ratio of modifying agent and microcrystalline cellulose is in mass ratio 1:1；Modification of microcrystalline fiber
Element is 3:7 with soybean oil based resin mass ratio；The dosage of initiator is the 2% of resin quality.
Embodiment 3
Raw material: microcrystalline cellulose (average particle size is 50 μm) is purchased from Thermo Fisher Scientific Inc.；Epoxy soybean
(average molecular weight is 1200 g/mol to oily acrylate (AESO)；Viscosity (25 DEG C): 18000 ~ 32000 mPas；Acid value:
≤ 10 mg KOH/g；Polymerization inhibitor: 3500 ~ 4500 ppm metoxyphenols), dimethylformamide (DMF), methacrylic anhydride
(MAA), 4-dimethylaminopyridine (DMAP) and peroxidized t-butyl perbenzoate (TBPB) be purchased from Sigma-Aldrich (on
Sea) trade Co., Ltd.
Modified microcrystalline cellulose enhances soybean oil based resin composite material:
The modifying process of modified microcrystalline cellulose are as follows: by the microcrystalline cellulose of 10 g, the methacrylic anhydride of 15 g and 0.5
The 4-dimethylaminopyridine of g is placed in the flask of the dimethylformamide containing 150 mL；Flask is then placed in ultrasonic water
In bath, 500 r/min of magnetic agitation, 60 DEG C of 2 h of reaction, ultrasonic power are 80 W；Solid is obtained by filtration after reaction
Product is through acetone, saturation NaHCO380 DEG C of 24 h of drying of vacuum are after solution and distilled water clean filtering 5 times repeatedly to get modification
Microcrystalline cellulose.
Composite material and preparation method thereof: the initiation of the modified microcrystalline cellulose of 30 g, the soybean oil based resin of 70 g, 1.4 g
Injection silica gel mould forms to obtain after agent and acetone are mixed evenly, the specific steps are as follows: by the modification of microcrystalline fiber of 30 g
Element is dispersed in the acetone of 100 mL under ultrasonic water bath auxiliary, and magnetic stirs 500 r/min, 5 min, ultrasonic power 80
W；Then the soybean oil based resin of 70 g is added and increases temperature to continuing to stir 10 min at 80 DEG C to remove acetone；It is cold
But to 1.4 g of initiator is added after room temperature and stirs cellulose-resin mixture liquor injection silica gel mould molding after 2 min, Gu
Change process is to be warming up to 160 DEG C after heating 2 h at 120 DEG C to continue to solidify 4 h；After cooling mold and take out sample, i.e.,
Obtaining modified microcrystalline cellulose enhances soybean oil based resin composite material.
In the preparation process, the amount ratio of modifying agent and microcrystalline cellulose is in mass ratio 1.5:1；Modification of microcrystalline is fine
Dimension element is 3:7 with soybean oil based resin mass ratio；The dosage of initiator is the 2% of resin quality.
Composite material bending property test:
The bending property of composite material is carried out according to ASTM D 790-10, size of sample: the mm of 80 mm × 10 ×
3.0 mm, test are completed on CMT6104 microcomputer controlled electronic universal tester.
The water imbibition of composite material is tested:
The water absorption test of composite material carries out under room temperature and boiling water respectively according to ASTM D 570 2005, sample rule
Lattice: the mm of mm × 3.0 of 80 mm × 10, test process are as follows: 1) room temperature is tested: sample is cold after 50 DEG C, 3 h drying
But it to room temperature, weighing, is subsequently dipped in distilled water place 24 h at room temperature；Sample is taken out after reaching the stipulated time, is dried, is claimed
Weight.2) boiling water is tested: sample being cooled to room temperature after 50 DEG C, 3 h drying, is weighed, is subsequently dipped to impregnate 2 h in boiling water；To
Sample is taken out after the arrival stipulated time and is placed in room temperature distilled water and stablizes 15 min, is taken out sample, is dried and weigh.
The bending strength of modified microcrystalline cellulose enhancing soybean oil based resin composite material
As shown in Figure 1, enhance soybean oil based resin composite material bending strength (16.73 with unmodified microcrystalline cellulose
MPa) compare, the bending strength for the composite material that the mass ratio of modifying agent and microcrystalline cellulose is 0.5,1 and 1.5 is respectively
19.66 MPa, 23.46 MPa and 27.98 MPa have been respectively increased 17.51%, 40.22% and 67.24%, modified composite wood
Compared with unmodified composite material, bending strength is significantly increased material.
The bending modulus of modified microcrystalline cellulose enhancing soybean oil based resin composite material
As shown in Figure 2, enhance soybean oil based resin composite material bending modulus (245.20 with unmodified microcrystalline cellulose
MPa) compare, the bending modulus for the composite material that the mass ratio of modifying agent and microcrystalline cellulose is 0.5,1 and 1.5 is respectively
324.58 MPa, 370.57 MPa and 433.94 MPa, have been respectively increased 32.37%, 51.13% and 76.97%, modified multiple
Compared with unmodified composite material, bending modulus is significantly increased condensation material.
The bending strain of modified microcrystalline cellulose enhancing soybean oil based resin composite material
From the figure 3, it may be seen that the bending strain with unmodified microcrystalline cellulose enhancing soybean oil based resin composite material
(12.88%) compare, the bending strain for the composite material that the mass ratio of modifying agent and microcrystalline cellulose is 0.5,1 and 1.5 is respectively
10.96%, 11.37%, 10.24%, 15%, 11.80%, 20.50% is reduced respectively.
As shown in Figure 4, the water absorption rate with unmodified microcrystalline cellulose enhancing soybean oil based resin composite material at room temperature
(1.14%) compare, the room temperature water absorption rate for the composite material that the mass ratio of modifying agent and microcrystalline cellulose is 0.5,1 and 1.5 is
0.87%, 0.80%, 0.63%, 23.88%, 30.45%, 44.71% is reduced respectively.Unmodified composite material boiling water water absorption rate is
2.50%, the boiling water water absorption rate for the composite material that the mass ratio of modifying agent and microcrystalline cellulose is 0.5,1 and 1.5 is respectively
2.14%, 2.02% and 1.89%, 14.38%, 19.45% and 24.60% is reduced respectively.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (5)
1. a kind of modified microcrystalline cellulose, it is characterised in that: the modified microcrystalline cellulose is by solvent, modifying agent, catalysis
The modification under ultrasonic wave booster action of agent and microcrystalline cellulose forms, and the modifying agent is methacrylic anhydride, modifying agent with
The mass ratio of microcrystalline cellulose is 0.5 ~ 1.5:1；The solvent is n,N-Dimethylformamide；The catalyst is 4- bis-
Methylamino pyridine；
Preparation method are as follows: microcrystalline cellulose, modifying agent and catalyst are placed in the flask containing solvent；Then flask is set
In ultrasound bath pot, magnetic agitation 500r/min, 60 DEG C of 2 h of reaction, ultrasonic power are 80 W；It crosses after reaction
Filter obtained solid product is after acetone, saturation NaHCO3 solution and distilled water clean filter 23 ~ 5 time repeatedly, 80 DEG C of dryings of vacuum
24 h are to get modified microcrystalline cellulose.
2. a kind of enhancing soybean oil based resin composite material prepared using modified microcrystalline cellulose described in claim 1,
Be characterized in that: the raw material including following parts by weight: 20 ~ 40 parts of modified microcrystalline cellulose, draws 60 ~ 80 parts of soybean oil based resin
1 ~ 7 part of agent of hair.
3. composite material according to claim 2, it is characterised in that: the raw material including following parts by weight: modification of microcrystalline
30 parts of cellulose, 70 parts of soybean oil based resin, 3 parts of initiator.
4. composite material according to claim 2, it is characterised in that: the soybean oil based resin is epoxidized soybean oil third
Olefin(e) acid ester；The initiator is peroxidized t-butyl perbenzoate.
5. a kind of method for preparing composite material as claimed in claim 2, it is characterised in that: by modified microcrystalline cellulose super
In acetone, and with 5 min of speed magnetic agitation of 500r/min, ultrasonic power is 80 W to the lower dispersion of sound wave auxiliary, is formed
Dispersion liquid；Then soybean oil based resin is added in dispersion liquid, increases temperature to 80 DEG C, continues to stir 10 min to remove third
Ketone；After then cooling to room temperature, initiator is added, and stir 2 min, obtains cellulose-resin mixture liquor；Then by cellulose-
Resin mixture liquor injects silica gel mould molding, and solidification temperature is 100 ~ 160 DEG C, and the time is 2 ~ 6 h；After cooling mold simultaneously
Taking out sample enhances soybean oil based resin composite material to get modified microcrystalline cellulose.
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| CN113527596B (en) * | 2021-07-31 | 2022-09-06 | 福建农林大学 | Photocuring 3D printing bamboo fiber reinforced palm oil-based composite material |
| CN115010862B (en) * | 2022-07-04 | 2023-09-12 | 南京林业大学 | Preparation method of cellulose-based ion conductive elastomer |
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| CN101693743A (en) * | 2009-10-28 | 2010-04-14 | 中国林业科学研究院林产化学工业研究所 | Process for preparing cellulose derivatives containing double-bond lateral group |
| CN104448793A (en) * | 2014-12-30 | 2015-03-25 | 福建农林大学 | Plant fiber reinforced modified soy-based resin composite material |
| CN104448846A (en) * | 2014-12-30 | 2015-03-25 | 福建农林大学 | Plant fiber reinforced soy-based resin composite material and preparation method thereof |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050239744A1 (en) * | 2004-04-22 | 2005-10-27 | Michael Ioelovich | Method of producing microcrystalline cellulose-containing compositions |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693743A (en) * | 2009-10-28 | 2010-04-14 | 中国林业科学研究院林产化学工业研究所 | Process for preparing cellulose derivatives containing double-bond lateral group |
| CN104448793A (en) * | 2014-12-30 | 2015-03-25 | 福建农林大学 | Plant fiber reinforced modified soy-based resin composite material |
| CN104448846A (en) * | 2014-12-30 | 2015-03-25 | 福建农林大学 | Plant fiber reinforced soy-based resin composite material and preparation method thereof |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
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